Continuous flow (Sulfated) Zirconia Catalysed Cascade Conversion of Levulinic Acid to γ‐Valerolactone

Abstract

γ-Valerolactone (GVL) is a renewable and versatile platform chemical derived from sustainable carbon feedstocks. The cascade conversion of levulinic acid into GVL requires Brønsted and Lewis acid catalysed reactions. Here, a dual-catalyst bed configuration is demonstrated that promotes synergy between Brønsted acid sites in sulfated zirconia (SZ) and Lewis acid sites in ZrO 2/SBA-15 for the liquid phase, continuous flow esterification and subsequent catalytic transfer hydrogenation (CTH) of levulinic acid to GVL. A saturated surface sulfate monolayer, possessing a high density of strong Brønsted acid sites, was optimal for levulinic acid esterification to isopropyl levulinate over SZ (>80 % conversion). A conformal ZrO 2 bilayer, deposited over a SBA-15 mesoporous silica and possessing mixed Brønsted:Lewis acidity, catalysed CTH of the levulinate ester and subsequent dealcoholisation/cyclisation to GVL (>60 % selectivity). Maximum stable productivity for the dual-bed was 2.2 mmol GVL.g cat.h −1 at 150 °C, significantly outperforming either catalyst alone or a physical mixture of both. Flow chemistry is a versatile approach to achieve spatial control over cascade transformations involving distinct catalytically active sites.

Publication DOI: https://doi.org/10.1002/cctc.202201224
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
Additional Information: Copyright © 2022, The Authors. ChemCatChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License [https://creativecommons.org/licenses/by-nc/4.0/], which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. Funding Information: The authors thank the Australian Research Council for financial support (DP200100204, DP200100313 and LE210100100), and Luxfer MEL Technologies for providing materials. Open Access publishing facilitated by RMIT University, as part of the Wiley ‐ RMIT University agreement via the Council of Australian University Librarians.
Uncontrolled Keywords: catalytic transfer hydrogenation,continuous flow reaction,dual-bed cascade,sulfated zirconia,γ-valerolactone,Catalysis,Physical and Theoretical Chemistry,Organic Chemistry,Inorganic Chemistry
Publication ISSN: 1867-3899
Last Modified: 13 Jun 2024 07:26
Date Deposited: 23 Jan 2023 11:42
Full Text Link:
Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
https://chemist ... /cctc.202201224 (Publisher URL)
PURE Output Type: Article
Published Date: 2022-12-19
Published Online Date: 2022-12-19
Accepted Date: 2022-12-19
Authors: Merenda, Andrea
Orr, Samantha Alana
Liu, Yang
Hernández Garcia, Blanca
Osatiashtiani, Amin (ORCID Profile 0000-0003-1334-127X)
Morales, Gabriel
Paniagua, Marta
Melero, Juan Antonio
Lee, Adam Fraser
Wilson, Karen

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